AN UNPRECEDENTED ELECTRONIC PREFERENCE FOR THE META PRODUCT IN DIELS-ALDER REACTIONS OF ETHYNYLDIALKYLBORANES - [(TRIMETHYLSILYL)ETHYNYL]-9-BBN AS A REACTIVE AND VERSATILE DIENOPHILE
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[(Trimethylsilyl)ethynyl]-9-BBN undergoes DielsAlder reactions with acyclic dienes at 100 C to afford 1,4-cyclohexadienes in high yields. The novel regiochemistry of these reactions is consistent with an ab initio prediction of advanced bonding to boron in a [4 atom + 3 atom] transition state. 1992, American Chemical Society. All rights reserved.